Method of deacidifying cellulose based materials

ABSTRACT

Provided are compositions and methods of deacidifying a cellulose-based material. The compositions include a hydrohalo-olefin and a deacidification agent dispersed within the hydrohalo-olefin. Cellulose-based materials are contacted with the composition for a sufficient time to increase the pH of the material.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application claims priority to U.S. Provisional Application Ser. No. 61/576,667, filed Dec. 16, 2011, the contents of which are incorporated herein by reference in its entirety.

FIELD OF THE INVENTION

The present invention relates, in part, to the deacidification of cellulose-based materials. In particular, the present invention relates to the use of hydrofluoro-olefins and/or hydrochlorofluoro-olefins to reduce the acidity associated with certain cellulose-based materials.

BACKGROUND OF THE INVENTION

The deterioration of paper, books, newspaper, and other cellulose-based materials is a problem of growing concern throughout the world. It has been estimated, for example, that of the approximately 20 million books in the collection of the Library of Congress, about 30% are in such a state of deterioration that they cannot be circulated. At the New York Library, it was discovered that nearly half of the more than five million books housed therein are subject to severe deterioration. In addition, it is estimated that 97% of all the books published between 1900 and 1949 have a useful life of no more than about 50 years.

A major cause associated with the deterioration of cellulose-based materials is the inherent acidity of such materials. The manufacture of paper and other cellulose materials often requires the addition of acids and acidic chemicals to reduce absorbency and to allow the paper products to accept inks and dyes. In addition, the manufacturing processes of these materials often include the introduction of additives via acidic mechanisms. Unfortunately, these manufacturing processes often result in cellulose-based products having residual acidic material. The cellulose-based products tend to have low pH values and, accordingly, tend to undergo slow, but relentless, acid deterioration.

U.S. Pat. No. 4,522,843 suggests that this problem can be solved by using a dispersion of a basic metal salt into a chlorofluorocarbon such as trichlorofluoromethane, trichlorotrifluoroethane and dichlorotetrafluoroethane and mixtures therof. In US 2003/0150571, the inventors point out that these substances are chlorofluorocarbons and contribute significantly to the depletion of the atmospheric ozone layer. They propose the use hydrofluorocarbons which do not contribute to the depletion of the ozone layer and also have physical properties that are appropriated for this application.

Since the time of that application, there has been growing concern about substances with high global warming potentials. Such substances have a direct contribution to global warming. Hydrofluorocarbons such as described in US2003/0150571 fall into this category. There is therefore a need for compositions that can be used for the deacidification of the cellulose materials.

SUMMARY OF THE INVENTION

In certain embodiments, the present invention relates to a deacidification composition comprising (a) dispersing medium comprising, and preferably comprising in major proportion by weight, one or more hydrohalo-olefin(s) and (b) a deacidification agent dispersed in the dispersing medium, and even more preferably dispersed in the one or more hydrohalo-olefin(s). Preferably, the one or more hydrohalo-olefin(s) contain from two to six carbon atoms, and more preferably in certain embodiments three to five carbon atoms. In further aspects, the one or more hydrohalo-olefin(s) have a boiling point or boiling range of from about −29.0° C. to about 50° C.

In certain preferred embodiments, the preferred hydrohalo-olefin of the present invention comprises a compound according to formula I

-   -   where each R is independently Cl, F, Br, I or H and at least one         R is a halogen and at least one R is a hydrogen;     -   R′ is (CR₂)_(n)Y;     -   Y is CRF₂; and     -   n is 0, 1, 2 or 3.         Such compounds include hydrofluoro-olefins, which may be         selected from the group consisting of a tetrafluoropropene, a         trifluoropropene, a heptafluorobutene, a heptafluoropentene, and         combinations thereof. Such compounds also include         hydrochlorofluoro-olefins, which may be provided as a         chlorotrifluoropropene. Non-limiting examples of such         hydrohalo-olefins include, but are not limited to, one or more         of HCFO-1233zd, HFO-1234ze, HFO-1234yf, HFO-1243zf, HFO-1327my,         HFO-1327cyc, HFO-1447fzy, HFO-1447fycc, including isomers         thereof. In certain embodiments, the hydrohalo-olefin includes         HCFO-1233zd.

Any known deacidification agent may be used according to the broad scope of the present invention. In preferred embodiments, the deacidification agent comprises metal oxides, metal hydroxides, metal carbonates, metal salts, and combinations of two or more thereof. In certain aspects, it is a Group IA or Group IIA metal, which may include Group IA or Group IIA metal oxides, metal hydroxides, metal carbonates, and combinations thereof. In certain preferred embodiments, the deacidification agent comprises magnesium oxide. In certain preferred embodiments, the deacidification agent is in particle form and may have a predominant particle size of from about 0.01 to about 1.0 micron.

The dispersing medium may include, in addition to the one or more hydrohalo-olefins, any one or more of several components in order to aid in, modulate and/or enhance the dispersing function or to provide any other desired function to the composition consistent with intended purpose. For example, the dispersing medium may also include one or more surfactants, which may be provided to aid dispersion of the deacidification agent within the hydrohalo-olefin. Such surfactants may include a fluorinated surfactant or any other surfactant able to obtain the effects provided herein.

The present invention also relates to methods of deacidifying a cellulose based material by providing a composition according to the present invention; and increasing the pH of a cellulose-based material by contacting said material with the composition. In certain embodiments, the contacting step may include immersing at least a portion of the cellulose-based material in the composition. The contacting step may also, or alternatively, include spraying the composition onto said cellulose-based material. The hydrohalo-olefin in preferred embodiments is then evaporated to deposit at least a portion of the deacidifying agent on the cellulose-based material.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates, in part, to compositions and methods of deacidifying cellulose-based materials that are not only adaptable for use with a wide range of deacidification agents, but also tend to be more environmentally-friendly and less costly than prior art processes. In one aspect, the present invention relates to the discovery that halogenated olefins, including hydrofluoro-olefins (“HFO”) and hydrochlorofluoro-olefins (“HCFO”), can be used in conjunction with a wide variety of basic materials to form compositions suitable for use in deacidifying acidic cellulosic materials.

Applicants have determined, for example, that halogenated olefins having a boiling point of, or mixtures or blends of halogenated olefins having a boiling range within, from about −29.0° C. to about 50° C. are capable of dispersing effective amounts of deacidifying agents therein such that the composition comprising the halogenated olefins and deacidifying agents may be advantageously introduced to acidic materials to increase the pH associated therewith. The preferred forms of the present compositions are similarly advantageous because they do not contribute to ozone depletion and have minimal ODP values. Thus, they are environmentally benign. The preferred halogenated olefins according to the present invention are also relatively volatile, and thus, can be removed easily from the cellulosic materials without the need to resort to conventional drying methods that are expensive and time-consuming. Unlike prior art deacidifying compositions, compositions of the present method are also relatively inexpensive, and exhibit additional beneficial properties such as, low flammability, low toxicity, and low reactivity.

As used herein, the term “hydrohalo-olefins” relates to any organic compound having at least one double bond between two carbon atoms, at least one halogen and at least one hydrogen. Such compounds are inclusive of, but not limited to, hydrofluoro-olefins and hydrochlorofluoro-olefins. As used herein, the term “hydrofluoro-olefin” or “HFO” relates to any organic compound having at least one double bond between two carbon atoms, at least one fluorine and at least one hydrogen. As used herein the term “hydrochlorofluoro-olefin” or “HCFO” relates to any organic compound having at least one double bond between two carbon atoms, at least one fluorine, at least one chlorine, and at least one hydrogen.

In certain aspects, the hydrohalo-olefin contains C2 to C6 carbon atoms, or C3 to C5 carbon atoms, wherein the double bond is between two of the carbons. As used herein, the term C2 to C6 refers to any olefin having from two to six carbon atoms in the backbone, and similarly the term C3 to C5 means any olefin having from three to five carbon atoms in the backbone.

In one aspect of the foregoing, the hydrohalo-olefin, hydrofluoro-olefin, and/or hydrochlorofluoro-olefin is compound according the following formula I:

-   -   where each R is independently Cl, F, Br, I or H and at least one         R is a halogen and at least one R is a hydrogen;     -   R′ is (CR₂)_(n)Y;     -   Y is CRF₂; and     -   n is 0, 1, 2 or 3.         In embodiments wherein the compound is a hydrofluoro-olefin, at         least one R is a hydrogen and at least one R is a fluorine. In         embodiments where the compound is a hydrochlorofluoro-olefin, at         least one R is a hydrogen, at least one R is a fluorine and at         least one R is a chlorine.

Useful hydrofluoro-olefins, in accordance with the foregoing, include but are not limited to one or more tetrafluoropropenes (HFO-1234), trifluoropropene (HFO-1243), heptafluorobutene (HFO-1327), heptafluoropentene (HFO-1447) and/or a fluorohexene. Useful hydrochlorofluoro-olefins, in accordance with the foregoing, include but are not limited to chlorotrifluoropropene (HCFO-1233) and/or a chlorofluorohexene.

In certain aspects, the hydrohalo-olefin, hydrofluoro-olefin and/or hydrochlorofluoro-olefin is substantially non-toxic. That is, in certain aspects, the hydrohalo-olefin, hydrofluoro-olefin and/or hydrochlorofluoro-olefin has a very low acute toxicity level, as measured by inhalation exposure to mice and/or rats.

The term “HFO-1234” is used herein to refer to all tetrafluoropropenes. Among the tetrafluoropropenes are included, but not limited to, 2,3,3,3-tetrafluoropropene (HFO-1234yf) or cis- and/or trans-1,1,1,3-tetrafluoropropene (HFO-1234ze). The term “HFO-1234ze” is used herein generically to refer to 1,1,1,3-tetrafluoropropene, independent of whether it is the cis- or trans- form. The terms “cisHFO-1234ze” and “transHFO-1234ze” are used herein to describe the cis- and trans- forms of 1,1,1,3-tetrafluoropropene respectively. The term “HFO-1234ze” therefore includes within its scope cisHFO-1234ze, transHFO-1234ze, and all combinations and mixtures of these. In certain aspects of the present invention, the hydrofluoro-olefin comprises, consists essentially of, or consists of cisHFO-1234ze. In further embodiments, the hydrofluoro-olefin comprises, consists essentially of, or consists of transHFO-1234ze, and in even further embodiments the hydrofluoro-olefin comprises, consists essentially of, or consists of cisHFO-1234ze and transHFO-1234ze.

The term “HCFO-1233” is used herein to refer to all trifluoromonochloropropenes. Among the trifluoromonochloropropenes are included, but not limited to, cis- and/or trans-1,1,1-trifluoro-3-chlororopropene (HCFO-1233zd). The terms “cisHCFO-1233zd” and “transHCFO-1233zd” are used herein to describe the cis- and trans- forms of 1,1,1-trifluoro-3-chlororopropene, respectively. The term “HCFO-1233zd” therefore includes within its scope cisHCFO-1233zd, transHCFO-1233zd, and all combinations and mixtures of these. In certain aspects of the present invention, the hydrochlorofluoro-olefin comprises, consists essentially of, or consists of cisHCFO-1233zd. In further embodiments, the hydrochlorofluoro-olefin comprises, consists essentially of, or consists of transHCFO-1233zd, and in even further embodiments the hydrochlorofluoro-olefin comprises, consists essentially of, or consists of cisHCFO-1233zd and transHFO-1233zd.

Specific preferred embodiments of such compounds are provided below in Table 1, but such compositions are not limiting to broad scope the invention. Compounds of the present invention may also include any and all isomers thereof and/or alternative compounds in accordance with the foregoing.

TABLE 1 HFO or HCFO Molecular formula NBP (° C.) HCFO-1233zd(E) CF3CH=CHCl 19.0 HFO-1234ze(E) CF3CH=CHF −19.0 HFO-1234ze(Z) CF3CH=CHF 9.0 HFO-1234yf CF3CF=CHF −28.0 HFO-1243zf CF3CH=CH2 −25.2 HCFO-1233zd(Z) CF3CH=CHCl 38.0 HFO-1327my(Z) CF3CF=CHCF3 8.0 HFO-1327cyc CF2=CFCF2CHF2 20-21 HFO-1447fzy CF3CF(CF3)CH=CH2 21-25 HFO-1447fycc CF2HCF2CF2CF=CH2 32.0 In certain embodiments, the compositions of the present invention include, and preferably in major proportion by weight, and even more preferably in certain embodiments consist essentially of 1233zd, which exhibits desirable non-flammability, non-toxicity and environmentally acceptability. Such compositions may include 1233zd, alone, or in combination with one or more of the foregoing hydrohalo-olefins, hydrofluoro-olefins, and/or hydrochlorofluoro-olefins.

The dispersing medium, and in particular the hydrohalo-olefin(s), may be provided in any effective amount to act as a carrier for the deacidification agent and deliver it to the target substrate of interest. In certain non-limiting aspects, the compositions of the present invention comprise greater than 50 wt % of one of more hydrohalo-olefins, based on the total weight of the composition. In further embodiments, the compositions comprise about 75 wt. % or more, about 80 wt. % or more, about 85 wt. % or more, about 90 wt. % or more, about 95 wt. % or more, or about 99 wt. % or more of the hydrohalo-olefin(s). In certain non-limiting embodiments, the hydrohalo-olefin(s) comprises from about 1 to about 99 weight percent of the composition, from about 50 to about 99 wt. % of the composition, from about 75 to about 99 wt. % of the composition, from about 80 to about 99 wt. % of the composition, from about 90 to about 99 wt. % of the composition, or from about 90 to about 95 wt. % of the composition, based on the total weight of the composition.

As noted above, compositions of the present invention include one or more deacidification agents. A “deacidification agent,” as used herein, means a basic substance that can be used in conjunction with one or more of the hydrohalo-olefins provided herein to deacidify cellulose-based materials. Examples include oxides, hydroxides, carbonates, and bicarbonates of zinc and metals in Group 1 and Group II of the Periodic Table. According to certain embodiments, the deacidification agents of the present invention are oxides, hydroxides, carbonates and bicarbonates of zinc, magnesium, sodium, potassium, calcium, or combinations of two or more thereof. Non-limiting examples of such agents include zinc carbonate, zinc bicarbonate, zinc oxide, magnesium carbonate, magnesium bicarbonate, magnesium oxide, magnesium methyl carbonate, calcium oxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and combinations of two or more thereof. More preferred, but non-limiting, deacidification agents include magnesium oxide and magnesium methyl carbonate. An especially preferred, but non-limiting, deacidification agent is magnesium oxide.

In certain embodiments, the deacidification agents of the present invention are used in particle form. According to certain embodiments, the deacidification agent particles are of a size suitable for being depositing on a cellulose-based material to cause deacidification of the material without substantially impairing images, if any, thereon. The predominant particle size (i.e. the size of from about 90 to about 99%, or from about 95 to about 99% of the particles) is from about 0.01 to about 1.0 micron. According to certain other embodiments, the predominant particle size is from about 0.2 to about 0.5 micron. The particle surface area is from about 50 to about 200 m²/g BET, from about 100 to about 200 m²/g, or about 170 m²/g.

A variety of deacidification agent particles suitable for use in the present invention are available commercially and/or can be prepared using processes known in the art. As will be recognized by those of skill in the art, processes for preparing alkaline metal particles include burning elemental metals and collecting the resulting smoke, attrition of preformed oxides, calcination of elemental salts, and the like. In light of the disclosure herein, those of skill in the art will readily be able to obtain deacidification agent particles suitable for use in the present invention.

The deacidification agent may be provided in any effective amount to achieve the objectives identified herein. In certain non-limiting aspects, the compositions of the present invention comprise about 50 wt % or less of the deacidification agent, based on the total weight of the composition. In further embodiments, the compositions comprise about 25 wt. % or less, about 20 wt. % or less, about 15 wt. % or less, about 10 wt. % or less, about 5 wt. % or less, or about 1 wt. % or less of the deacidification agent. In certain non-limiting embodiments, the deacidification agent comprises from about 1 to about 99 weight percent of the composition, from about 1 to about 50 wt. % of the composition, from about 1 to about 25 wt. % of the composition, from about 1 to about 15 wt. % of the composition, from about 1 to about 10 wt. % of the composition, or from about 5 to about 10 wt. % of the composition, based on the total weight of the composition.

According to certain embodiments, the compositions used in the present invention further comprise a surfactant, which may aid in the dispersion of the dacidification agent in the hydrohalo-olefin. Any of a wide range of surfactants are suitable for use in the present invention and may include, but are not limited to ionic surfactants, anionic surfactants, cationic surfactants, and/or non-ionic surfactants, any one of which may optionally be halogenated. In certain aspects, preferred, but non-limiting, surfactants used in the present invention are fluorinated surfactants, such as, for example, Fluorad, FC740 (approximately 50% petroleum naptha and 50% fluoroaliphatic polymeric esters) and FC721 available commercially from 3M and Solsperse 3000 and 6000 available from ICI Corporation.

The amounts of deacidification agent, hydrohalo-olefin, and surfactant to be used for any particular application will depend on a number of factors including the length of treatment of the cellulose material with the deacidification composition and the amount of deposition of deacidification agent required. In general, it is desirable that an effective amount of deacidification agent is used with a given hydrohalo-olefin such that the resulting composition contains a minimum concentration of agent dispersed therein over at least the length of time needed to deposit the agent on cellulosic material. In certain embodiments, the addition of a surfactant may help increase the dispersibility of deacidification agent in the hydrohalo-olefin.

According to certain embodiments, the concentration of the deacidification agent in the composition is from about 0.001 to about 0.5 weight percent based on the total weight of the compositions. According to other embodiments, the deacidification agent concentration is from about 0.01 to about 0.4 weight percent.

According to certain embodiments, the surfactant has a concentration of from about 0.005 to about 1.0 weight percent based on the total weight of the deacidifying composition. Alternatively, the concentration is from about 0.005 and 0.5 weight percent.

In light of the disclosure contained herein those of skill in the art will readily be able to formulate HFC/deacidification agent compositions suitable for use in a wide range of applications of the present invention.

The contacting step of the present invention involves contacting at least a portion of a cellulose-based material with a composition of the present invention to increase the pH associated with the cellulose material. Any of a wide range of cellulose-based materials can be used in the present methods. For example, suitable materials include paper and paper products, books, wood and wood products, combinations of two or more thereof, and the like.

Any of a wide range of methods for contacting the acidic cellulose material with a composition of the present invention can be used. Examples of suitable contacting methods include immersion of the cellulose material in the composition, adding the composition dropwise to the cellulose material, spraying the composition onto the cellulose material, combinations of two or more thereof, and the like. In aspects where the composition is applied as a sprayable composition, it may be provided as an aerosol using any of the foregoing or otherwise known propellants.

Optionally, the use of electrostatic attraction may be used in conjunction with the above methods to enhance deposit of materials on paper. According to certain embodiments, the step of contacting the cellulose material involves contacting substantially the entire surface area of the cellulose material with the composition such that removal of the composition results in lowering the acidity of the cellulose material.

The contacting step of the present invention may further comprise the step of removing the hydrohalo-olefin from the cellulosic material to deposit at least a portion of the deacidification agent on the cellulosic material. Any known methods for removing the hydrohalo-olefin may be used according to the present invention. In certain embodiments, the removing step comprises evaporating the hydrohalo-olefin from the cellulosic material. According to certain embodiments, the evaporating step comprises changing the pressure and/or temperature to which the hydrohalo-olefin and cellulosic material are exposed such that the hydrohalo-olefin is converted to the gaseous state.

Once a cellulose material has been deacidified according to the present invention, the removed hydrohalo-olefin solvent can be recycled for further use. In this manner, the present invention allows for the deacidification of cellulosic materials without the need for time-consuming solvent-removing drying steps and excess clean-up.

The present invention is more fully illustrated by the following non-limiting examples. It will be appreciated that variations in proportions and alternatives in elements of the components of the invention will be apparent to those skilled in the art and are within the scope of the invention.

EXAMPLES Example 1

This example illustrates one method of deacidifying paper according to the present invention.

One thousand (1000) grams of 1233zd are mixed with 3.2 grams of magnesium oxide and 0.8 grams of surfactant FC-740. The mixture is placed in a 2 liter beaker and stirred. A cooling coil is placed on the lip of the beaker to condense and recirculate 1233zd vapor. Four samples of 63 year old paper are prepared and the acidity of each sample is measured using the TAPPI509 om-96 method, a copy of a document describing this method is attached hereto and is incorporated herein by reference. The pH measurement of each sample is about 4.6. Each sample is dipped in the mixture in the beaker for twenty seconds and allowed to dry for 5 minutes. The solvent evaporates off very quickly. The pH of each sample is then measured. The average pH of the four samples is about 8.9

Example 2

This example illustrates another method of deacidifying paper according to the present invention.

A 150 cc aerosol can is loaded with 50 grams of a suspension prepared according to Example 1. One of HFC-134a (1.5 grams), HFO-1243zf, HFO-1234ze(E), (1.5 grams) or HFO-1234yf (1.5 grams) is added to the can to act as a propellant for the suspension. A sample of 63 year old paper as described in Example 1 is sprayed with the suspension from the aerosol can. The pH of the paper after spraying is measured to be 9.0

Example 3

This example illustrates one method of deacidifying paper according to the present invention.

One thousand (1000) grams of 1234ze(Z) are mixed with 3.2 grams of magnesium oxide and 0.8 grams of surfactant FC-740. The mixture is placed in a 2 liter beaker which is kept at 0° C. and stirred. A cooling coil is placed on the lip of the beaker to condense and recirculate 1233zd vapor. Four samples of 63 year old paper are prepared and the acidity of each sample is measured using the TAPPI509 om-96 method, a copy of a document describing this method is attached hereto and is incorporated herein by reference. The pH measurement of each sample is about 4.6. Each sample is dipped in the mixture in the beaker for twenty seconds and allowed to dry for 5 minutes. The solvent evaporates off very quickly. The pH of each sample is then measured. The average pH of the four samples is about 8.9

Example 4

This example illustrates another method of deacidifying paper according to the present invention.

A 150 cc aerosol can is loaded with 50 grams of a suspension prepared according to Example 3. One of HFC-134a (1.5 grams), HFO-1243zf, HFO-1234ze(E) (1.5 grams) or HFO-1234yf (1.5 grams) is added to the can to act as a propellant for the suspension. A sample of 63 year old paper as described in Example 1 is sprayed with the suspension from the aerosol can.

The pH of the paper after spraying is measured to be 9.0

Example 5

This example illustrates one method of deacidifying paper according to the present invention.

One thousand (1000) grams of 1327cyc are mixed with 3.2 grams of magnesium oxide and 0.8 grams of surfactant FC-740. The mixture is placed in a 2 liter beaker and stirred. A cooling coil is placed on the lip of the beaker to condense and recirculate 1233zd vapor. Four samples of 63 year old paper are prepared and the acidity of each sample is measured using the TAPPI509 om-96 method, a copy of a document describing this method is attached hereto and is incorporated herein by reference. The pH measurement of each sample is about 4.6. Each sample is dipped in the mixture in the beaker for twenty seconds and allowed to dry for 5 minutes. The solvent evaporates off very quickly. The pH of each sample is then measured. The average pH of the four samples is about 8.9

Example 6

This example illustrates another method of deacidifying paper according to the present invention.

A 150 cc aerosol can is loaded with 50 grams of a suspension prepared according to Example 5. One of HFC-134a (1.5 grams), HFO-1243zf, HFO-1234ze (E) (1.5 grams) or HFO-1234yf (1.5 grams) is added to the can to act as a propellant for the suspension. A sample of 63 year old paper as described in Example 1 is sprayed with the suspension from the aerosol can. The pH of the paper after spraying is measured to be 9.0 

What is claimed:
 1. A method of deacidifying a cellulose based material comprising: providing a composition comprising a hydrohalo-olefin and a deacidification agent dispersed in said hydrohalo-olefin; and increasing the pH of a cellulose-based material by contacting said material with the composition.
 2. The method of claim 1 wherein said hydrohalo-olefin includes about two to about six carbon atoms.
 3. The method of claim 1 wherein said hydrohalo-olefin includes about three to about five carbon atoms.
 4. The method of claim 1 wherein said hydrohalo-olefin has a boiling point of from about −29.0° C. to about 50° C.
 5. The method of claim 1 wherein said hydrohalo-olefin is a compound according to formula I

where each R is independently Cl, F, Br, I or H and at least one R is a halogen and at least one R is a hydrogen; R′ is (CR₂)_(n)Y; Y is CRF₂; and n is 0, 1, 2 or
 3. 6. The method of claim 1 wherein said hydrohalo-olefin is a hydrofluoro-olefin.
 7. The method of claim 6 wherein the hydrofluoro-olefin is selected from the group consisting of a tetrafluoropropene, a trifluoropropene, a heptafluorobutene, a heptafluoropentene, and combinations thereof.
 8. The method of claim 1 wherein the hydrohalo-olefin is a hydrochlorofluoro-olefin.
 9. The method of claim 8 wherein the hydrochlorofluoro-olefin is a chlorotrifluoropropene.
 10. The method of claim 1 wherein the hydrohalo-olefin is selected from the group consisting of HCFO-1233zd, HFO-1234ze, HFO-1234yf, HFO-1243zf, HFO-1327my, HFO-1327cyc, HFO-1447fzy, HFO-1447fycc,
 11. The method of claim 10 wherein the hydrohalo-olefin is HCFO-1233zd.
 12. The method of claim 1 wherein said deacidification agent is in particle form.
 13. The method of claim 12 wherein said deacidification agent particles have a predominant particle size of from about 0.01 to about 1.0 micron.
 14. The method of claim 12 wherein said deacidification agent is selected from the group consisting of metal oxides, metal hydroxides, metal carbonates, metal salts, and combinations of two or more thereof.
 15. The method of claim 12 wherein said deacidification agent is selected from the group consisting of oxides, hydroxides, carbonates, and combinations of two or more thereof, of Group IA or Group IIA metals.
 16. The method of claim 15 wherein said deacidification agent is magnesium oxide.
 17. The method of claim 1 wherein said composition further comprises a surfactant.
 18. The method of claim 17 wherein said surfactant is a fluorinated surfactant.
 19. The method of claim 1 wherein said contacting step comprises immersing at least a portion of said cellulose-based material in said composition.
 20. The method of claim 1 wherein said contacting step comprises spraying said composition onto said cellulose-based material.
 21. The method of claim 1 wherein said increasing step further comprises evaporating the hydrohalo-olefin from said material subsequent to said contacting step to deposit at least a portion of said deacidifying agent on said cellulose-based material.
 22. A deacidification composition comprising; a hydrohalo-olefin; and a deacidification agent dispersed in said hydrohalo-olefin.
 23. The method of claim 22 wherein said hydrohalo-olefin includes about two to about six carbon atoms.
 24. The method of claim 22 wherein said hydrohalo-olefin includes about three to about five carbon atoms.
 25. The method of claim 22 wherein said hydrohalo-olefin has a boiling point of from about −29.0° C. to about 50° C.
 26. The method of claim 22 wherein said hydrohalo-olefin is a compound according to formula I

where each R is independently Cl, F, Br, I or H and at least one R is a halogen and at least one R is a hydrogen; R′ is (CR₂)_(n)Y; Y is CRF₂; and n is 0, 1, 2 or
 3. 27. The method of claim 22 wherein said hydrohalo-olefin is a hydrofluoro-olefin.
 28. The method of claim 27 wherein the hydrofluoro-olefin is selected from the group consisting of a tetrafluoropropene, a trifluoropropene, a heptafluorobutene, a heptafluoropentene, and combinations thereof.
 29. The method of claim 22 wherein the hydrohalo-olefin is a hydrochlorofluoro-olefin.
 30. The method of claim 29 wherein the hydrochlorofluoro-olefin is a chlorotrifluoropropene.
 31. The method of claim 22 wherein the hydrohalo-olefin is selected from the group consisting of HCFO-1233zd, HCFO-1233zd, HFO-1234ze, HFO-1234yf, HFO-1243zf, HFO-1327, HFO-1447, isomers thereof and combinations thereof.
 32. The method of claim 31 wherein the hydrohalo-olefin is HCFO-1233zd.
 33. The composition of claim 22 wherein said deacidification agent is selected from the group consisting of metal oxides, metal hydroxides, metal carbonates, metal salts, and combinations of two or more thereof.
 34. The composition of claim 22 wherein said deacidification agent is selected from the group consisting of oxides, hydroxides, carbonates, and combinations of two or more thereof, of Group IA or Group IIA metals.
 35. The composition of claim 22 wherein said deacidification agent comprises magnesium oxide.
 36. The composition of claim 22 wherein said composition further comprises a surfactant.
 37. The composition of claim 36 wherein said surfactant is a fluorinated surfactant. 